CN109881217B - Carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition and preparation method thereof - Google Patents
Carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition and preparation method thereof Download PDFInfo
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Abstract
Carbon fiber-based amorphous Pb-Mn-RuO for manganese electrodepositionxThe anode comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4Bottom layer, Sn-Co-RuO coated on the bottom layerxIntermediate layer and coating layer on Sn-Co-RuOxAmorphous Pb-Mn-RuO on intermediate layerxAnd an active layer. The carbon fiber-based amorphous Pb-Mn-RuO prepared by the inventionxCompared with the traditional lead-based multi-element alloy, the gradient anode material has the advantages that the service life and the conductivity of the anode are obviously prolonged on the basis of manganese chloride system anion diaphragm electro-deposition of manganese and no change of the structure of an electrolytic cell, the composition of electrolyte and the operation specification, the cell voltage can be reduced by more than 20%, the current efficiency is improved by 4-8%, and the generation of chlorine can be inhibited.
Description
Technical Field
The invention relates to the technical field of anode materials and preparation methods thereof, in particular to a preparation method of an anode material applied to extraction of nonferrous metals in an ammonium chloride system.
Background
Since hydrometallurgy has the advantages of high comprehensive utilization rate of resources, environment-friendly process, strong adaptability of low-grade ores and the like, the proportion of non-ferrous metals such as Cu, Zn, Ni, Mn and the like extracted by a wet method is gradually increased. In the electrolysis of non-ferrous metals, about 90% zinc, about 30% copper and 100% manganese are extracted by hydrometallurgical techniques. Taking wet-process manganese electrolysis as an example, the current efficiency of electrolytic manganese metal is low, generally only reaches about 75%, the electric energy consumption of each ton of electrolytic manganese product is nearly 6200 kW.h, the manganese metal is a famous 'electric tiger', and if the manganese metal is produced into 140 million tons of manganese ingots every year, the required energy consumption is close to 86.8 hundred million DEG C electricity. In the production process of electrolytic manganese metal, more than 95% of power consumption is concentrated on an electrolytic cell, and in the manganese electrolytic extraction process, the properties of anode materials directly influence the indexes such as ion discharge potential, overpotential change, current efficiency, electric energy consumption, anode service life, cathode product quality and the like.
The anode plate for electrolytic manganese production originally used graphite electrolysis, but was rejected because of its easy expansion and falling off during electrolysis, and the lead alloy plate was used in electrolytic manganese industry because of its easy shaping and stable operation in sulfuric acid electrolyte, and the electrolysis using the lead alloy plate is a large amount of fine particles MnO generated in the anode solution2，MnO2Lead on the surface of the lead alloy is precipitated and enters into the metal manganese through cathode electrodeposition by divalent lead ions, so that the purity of electrolytic manganese is reduced, crystal branches are formed on the surface of the metal manganese to short circuit a cathode and an anode, the electric energy consumption is large, and the direct current efficiency is reduced; meanwhile, the lead electrode is easy to bend and deform, the current efficiency is reduced, and the service life of the electrode is shortened. The titanium plate has good conductivity, larger strength and strong corrosion resistance, and is hardly influenced by dilute sulfuric acid and dilute hydrochloric acidAnd most organic acids such as chlorine gas, etc., and the quality is much smaller than that of lead plates. However, since pure titanium plates are easily passivated at low temperature and the conductivity of electrode plates is deteriorated, the surface of the titanium plate needs to be treated, and the titanium-based coating is expensive, so that one-time investment is large when industrialization is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition, which has the advantages of good electrocatalytic activity, strong electrode conductivity, low cell voltage in electrodeposition, long service life and low energy consumption. The invention also provides a preparation method of the anode material.
The purpose of the invention is realized by the following technical scheme:
a carbon fiber based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer.
The Ni-Co of the invention3O4The bottom layer is a composite coating, and Co in the composite coating3O4The composition is 2.85-10 wt%; the Sn-Co-RuOx intermediate layer is a plating layer, and the Sn: co: the Ru molar ratio is (54-80): (18-32): (1-10); pb in the amorphous Pb-Mn-RuOx active layer: mn: the Ru molar ratio is (42-70): (24-48): (2-12). The total thickness of the anode is 2-10 mm, wherein the thickness of the bottom layer is 20-200 mu m, the thickness of the middle layer is 10-100 mu m, and the thickness of the active layer is 0.1-1 mm.
The preparation method of the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition comprises the following steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, heating a carbon fiber substrate at 400-800 ℃ under the protection of nitrogen to increase the active specific surface of the carbon fiber and simultaneously avoid the breakage and damage of the carbon fiber in the treatment process, and then placing the carbon fiber substrate in H with the temperature of 40-90 ℃ and the mass percent concentration of 10-20%2SO4Oxidizing in the aqueous solution for 1-2 h to enable the surface of the solution to be in a stripe shape;
(2)Ni-Co3O4preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a neutral nickel plating solution, controlling the temperature to be 30-60 ℃, and controlling the cathode current density to be 0.5-2A/dm2Performing electrodeposition for 30-120 min to obtain active nickel, washing with deionized water, immediately placing into a cobalt salt gel solution, standing and growing for 4-8 h at 40-80 ℃ to obtain a zeolite imidazole frame, and then placing into a muffle furnace to control the temperature to be 400-600 ℃ to calcine for 2-6 h to obtain Ni-Co3O4A bottom layer;
(3) preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: solvent: the molar ratio of the metal chloride is 1-3: 5-8: 0.1-1 gel liquid is coated on the Ni-Co of the carbon fiber substrate treated in the step (2)3O4Drying the surface of the bottom layer for 10min at the temperature of 130 ℃, then putting the bottom layer into a muffle furnace, calcining for 4-20 min at the temperature of 300-500 ℃, repeating the process for 10 times, and calcining for 2h for the last time to obtain an Sn-Co-RuOx intermediate layer;
(4) preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate with the Sn-Co-RuOx intermediate layer obtained after the treatment in the step (3) in a lead methylsulfonate solution, and controlling the current density of the anode to be 1-4A/dm2And carrying out electrodeposition for 1-4 h at the temperature of 30-70 ℃ to obtain a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating for 1-3 h at the temperature of 100-300 ℃ to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode.
In the above steps, the neutral nickel plating solution comprises the following components in parts by weight: 150-200 g/L of nickel sulfate, 12-16 g/L of potassium chloride, 30-35 g/L of boric acid, 60-140 g/L of anhydrous potassium sulfate, 40-60 g/L of sodium citrate, 0.1-0.4 g/L of sodium dodecyl sulfate, and the pH value is controlled to be 4.5-6. The cobalt salt gel solution is prepared by mixing about 6g of cobalt nitrate and 2-methylimidazole according to the mass percentage of (20-60): (40-80) dissolving in 300-800 ml of methanol, fully stirring and standing to obtain the product. The solvent used for preparing the intermediate layer is one or two of ethylene glycol, ethanol, isopropanol and n-butanol; the metal chloride is one or two of tin chloride, cobalt chloride and ruthenium chloride; the lead methylsulfonate solution comprises the following components in percentage by weight: 100-300 g/L lead methylsulfonate, 50-100 g/L manganese methylsulfonate, 10-30 g/L ruthenium chloride, 60-140 g/L complexing agent and 10-30 g/L methanesulfonic acid. The complexing agent is one or more than two of sodium ethylene diamine tetracetate, acetylacetone, ascorbic acid and sodium acetate.
The invention eliminates the defects of low current efficiency, high energy consumption, serious pollution and the like of a sulfate system, and adopts chloride (MnCl)2－NH4Cl－H2O) electrolytic system, make full use of its electrolyte conductivity high, manganese deposit high efficiency, production tank advantage low, through the amorphous Pb-Mn-RuOx oxide layer with high activity and corrosion resistance, can play the effect of inhibiting chlorine and inhibiting the production of anode mud at the same time, solve the chlorine electrolytic system of chloride but overflow of the chlorine of anode and overflow the chlorine to the corrosion problem of the anode. The carbon fiber substrate has the good performances of high strength, low density, good chlorine corrosion resistance and the like, overcomes the defects of large surface inertia, low surface energy, lack of functional groups with catalytic activity, weak reaction activity and the like of the carbon fiber by plating the active layer on the surface of the carbon fiber, and effectively improves the performance of the whole anode material.
Compared with the prior art, the invention has the following advantages:
1. adopting light carbon fiber as a matrix, electrodepositing metal Ni after the matrix is pretreated, firmly combining Ni and C, then growing a zeolite imidazole frame on the surface of Ni and calcining cobalt salt to obtain the hydrochloric acid resistant Ni-Co3O4The bottom layer improves the binding force of the interface and the corrosion resistance of the plating layer, and prolongs the service life of the anode.
2、Ni-Co3O4Underlayer and Sn-Co-RuOXThe intermediate layers contain cobalt, the deviation of ionic radius between the cobalt and the cobalt is less than 30%, a gradient solid solution is easily formed, the interface resistance of each oxide layer is greatly reduced, and the conductivity of the electrode is improved.
3. In Sn-Co-RuOXOn the intermediate layer, an amorphous Pb-Mn-RuOx active layer with firm combination is obtained by electrochemical deposition and thermal decomposition, and after thermal decompositionPromote MnO2And PbO2Mutually diffuse, improve MnO2And PbO2And (4) mutual binding force.
4. The amorphous Pb-Mn-RuOx has nanocrystalline grains, larger specific surface area, smaller electron transfer resistance and more crystal defects, thereby generating better catalytic performance.
5. The anode can avoid the phenomenon that the coating is easy to fall off when the base body is passivated and is subjected to external force, and the service life of the electrode is prolonged.
6. In an anion membrane electrolytic cell, an amorphous Pb-Mn-RuOx oxide layer with high activity and corrosion resistance is found in a chloride system, so that the effects of inhibiting chlorine and inhibiting the generation of anode mud can be achieved, the production efficiency of electrolytic manganese is greatly improved, and the clean and efficient production of electrolytic manganese is realized.
7. The novel carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material is operated in a manganese chloride-containing system, has good corrosion resistance, can be used for preparing high-grade cathode products, has long service life and low material cost, can reduce the cell voltage by more than 20 percent, improves the current efficiency by 4 to 8 percent, and is impossible to achieve by lead electrodes.
Drawings
FIG. 1 is a surface topography of a carbon fiber after pretreatment;
FIG. 2 is a surface topography of carbon fiber/Ni;
FIG. 3 is a surface topography of carbon fiber/Ni/ZIF 67;
FIG. 4 is a carbon fiber/Ni-Co3O4The surface topography of (2).
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1
The carbon fiber based amorphous Pb-Mn-RuOx gradient anode material of the embodiment comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer. The Ni-Co3O4The bottom layer is a composite coating, and Co in the composite coating3O42.85-10 wt%, and the intermediate layer is Sn: co: the Ru molar ratio is (54-80): (18-32): (1-10); pb in the amorphous Pb-Mn-RuOx active layer: mn: the Ru molar ratio is (42-70): (24-48): (2-12).
The preparation method of the carbon fiber based amorphous Pb-Mn-RuOx gradient anode material comprises the following specific steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, heating a carbon fiber substrate at 400-800 ℃ under the protection of nitrogen to increase the active specific surface of the carbon fiber and simultaneously avoid the breakage and damage of the carbon fiber in the treatment process, and then placing the carbon fiber substrate at the temperature of 40-90 ℃ and the mass percent concentration of 10-20% of H2SO4Oxidizing the mixture in the aqueous solution for 1 to 2 hours to enable the surface of the mixture to be in a stripe shape.
(2)Ni-Co3O4Preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a neutral nickel plating solution, controlling the temperature to be 30-60 ℃, and controlling the cathode current density to be 0.5-2A/dm2Performing electrodeposition for 30-120 min to obtain active nickel, washing with deionized water, immediately placing into a cobalt salt gel solution, standing and growing for 4-8 h at 40-80 ℃ to obtain a zeolite imidazole framework (ZIF67), and then placing into a muffle furnace to control the temperature to be 400-600 ℃ and calcining for 2-6 h to obtain Ni-Co3O4A bottom layer; the neutral nickel plating solution comprises the following components in percentage by weight: 150-200 g/L nickel sulfate (NiSO)4·7H2O), 12-16 g/L potassium chloride (KC1), 30-35 g/L boric acid (H)3BO3) 60-140 g/L anhydrous potassium sulfate (K)2SO4) 40-60 g/L sodium citrate, 0.1-0.4 g/L sodium dodecyl sulfate, and pH controlled at 4.5-6. Preparing the cobalt salt gel liquid: weighing about 6g of cobalt nitrate and 2-methylimidazole, wherein the weight percentage of the cobalt nitrate and the 2-methylimidazole is (20-60): (40-80) dissolving in 300-800 ml of methanol, fully stirring, and standing to obtain a gel solution.
(3) Preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: solvent: the molar ratio of the metal chloride is 1-3: 5-8: 0.1-1 part of gel solution is coated on the plating obtained in the step (2)Ni-Co3O4And drying the surface of the carbon fiber substrate of the bottom layer for 10min at the controlled temperature of 130 ℃, then putting the surface into a muffle furnace, calcining for 4-20 min at the controlled temperature of 300-500 ℃, repeating the process for 10 times, and calcining for 2h at the last time to obtain the Sn-Co-RuOx intermediate layer. The solvent is one or two of ethylene glycol, ethanol, isopropanol and n-butanol. The metal chloride is one or more of tin chloride, cobalt chloride and ruthenium chloride.
(4) Preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate obtained in the step (3) in a lead methylsulfonate solution, and controlling the current density of an anode to be 1-4A/dm2And carrying out electrodeposition for 1-4 h at the temperature of 30-70 ℃ to obtain a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating for 1-3 h at the temperature of 100-300 ℃ to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode. The lead methanesulfonate solution comprises the following components in percentage by weight: 100-300 g/L lead methylsulfonate, 50-100 g/L manganese methylsulfonate, 10-30 g/L ruthenium chloride, 60-140 g/L complexing agent and 10-30 g/L methanesulfonic acid. The complexing agent is one or more than two of sodium ethylene diamine tetracetate, acetylacetone, ascorbic acid and sodium acetate.
The total thickness of the anode prepared by the embodiment is 2-10 mm, wherein the thickness of the bottom layer is 20-200 μm, the thickness of the middle layer is 10-100 μm, and the thickness of the active layer is 0.1-1 mm.
Example 2
The carbon fiber based amorphous Pb-Mn-RuOx gradient anode material of the embodiment comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer. Wherein, Ni-Co3O4Co in composite coating3O4Composition of 8 wt%, Sn in Sn-Co-RuOx plating layer: co: the molar ratio of Ru is 60: 28: 10; pb in the amorphous Pb-Mn-RuOx active layer: mn: the molar ratio of Ru is 50: 36: 10.
the preparation method of the carbon fiber based amorphous Pb-Mn-RuOx gradient anode material comprises the following specific steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, heating at 500 ℃ under the protection of nitrogen to increase the active specific surface of the carbon fiber and simultaneously avoid the breakage and damage of the carbon fiber in the treatment process, and then placing the carbon fiber substrate at the temperature of 60 ℃ and the mass percentage concentration of 15 percent H2SO4Is oxidized for 1.5h, so that the surface of the solution is in a stripe shape (see figure 1).
(2)Ni-Co3O4Preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a neutral nickel plating solution, controlling the temperature to be 40 ℃, and controlling the cathode current density to be 1A/dm2Electrodepositing for 120min to obtain active nickel (see figure 2), washing with deionized water, immediately placing into cobalt salt gel solution, standing at 60 deg.C for 6h to obtain zeolite imidazole framework (ZIF67) (see figure 3), calcining in muffle furnace at 500 deg.C for 4h to obtain Ni-Co3O4The bottom layer (see fig. 4). The neutral nickel plating solution comprises the following components in parts by weight: 180g/L nickel sulfate (NiSO)4·7H2O), 14g/L potassium chloride (KC1), 30g/L boric acid (H)3BO3) 80g/L anhydrous potassium sulfate (K)2SO4) 50g/L of sodium citrate and 0.2g/L of sodium dodecyl sulfate, and the pH value is controlled to be about 5. The cobalt salt gel solution is prepared by weighing about 6g of cobalt nitrate and 2-methylimidazole according to the mass percentage of 40: 60 dissolved in 400ml of methanol, fully stirred and then kept stand to obtain gel liquid.
(3) Preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: ethylene glycol: the molar ratio of metal chloride salt (mixture of tin chloride, cobalt chloride and ruthenium chloride) is 1: 6: 0.6 of gel solution is coated on the Ni-Co plated film obtained in the step (2)3O4And drying the surface of the carbon fiber substrate of the bottom layer for 10min at the controlled temperature of 130 ℃, then putting the surface into a muffle furnace to calcine for 10min at the controlled temperature of 400 ℃, repeating the process for 10 times, and finally calcining for 2h to obtain the Sn-Co-RuOx intermediate layer.
(4) Preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate plated with the Sn-Co-RuOx middle layer obtained in the step (3) in a lead methylsulfonate solution, and controlling the anode current density to be 2A/dm2Electrodepositing for 2 hours at the temperature of 50 ℃,obtaining a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating at 200 ℃ for 2h to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode. The lead methylsulfonate solution comprises the following components in percentage by weight: 200g/L lead methylsulfonate, 80g/L manganese methylsulfonate, 30g/L ruthenium chloride, 120g/L acetylacetone and 20g/L methanesulfonic acid.
The total thickness of the anode prepared in this example was 10mm, wherein the thickness of the bottom layer was 100 μm, the thickness of the intermediate layer was 50 μm, and the thickness of the active layer was 0.5 mm.
The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material prepared in the embodiment is placed in a manganese chloride electrolyte, and manganese is electrodeposited in an anion exchange membrane electrolytic cell under the electrolysis conditions that the concentration of manganese ions in a cathode electrolyte is 1mol/L, the concentration of ammonium chloride is 2mol/L, the electrolysis temperature is-10 ℃, and the current density is 500A/m2The pH value is 6.10, the concentration of the ammonium chloride in the anolyte is 2mol/L, the hydrochloric acid is 1mol/L, the electrical efficiency is improved by 8 percent compared with the traditional lead-silver alloy anode plate, the cell voltage can be reduced by 25 percent, and the service life is prolonged by 3 times.
Example 3
The carbon fiber based amorphous Pb-Mn-RuOx gradient anode material of the embodiment comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer. Wherein Ni-Co3O4Co in composite coating3O4Composition of 2.85 wt%, Sn in Sn-Co-RuOx plating layer: co: the molar ratio of Ru is 54: 18: 1; pb in the amorphous Pb-Mn-RuOx active layer: mn: the molar ratio of Ru is 42: 24: 12.
the preparation method of the carbon fiber based amorphous Pb-Mn-RuOx gradient anode material comprises the following specific steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, heating the carbon fiber substrate at 800 ℃ under the protection of nitrogen to increase the active specific surface of the carbon fiber and simultaneously avoid the breakage and damage of the carbon fiber in the treatment process, and then placing the carbon fiber substrate at the temperature of 40 ℃ and the mass percent concentration of 10% H2SO4Oxidizing for 2h in the aqueous solution of (1) to form a striped surface.
(2)Ni-Co3O4Preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a neutral nickel plating solution, controlling the temperature to be 30 ℃, and controlling the cathode current density to be 0.5A/dm2Electrodepositing for 30min to obtain active nickel, washing with deionized water, immediately placing into cobalt salt gel solution, standing at 40 deg.C for 8 hr to obtain zeolite imidazole framework (ZIF67), calcining in muffle furnace at 400 deg.C for 6 hr to obtain Ni-Co3O4A bottom layer. The neutral nickel plating solution comprises the following components in percentage by weight: 150g/L Nickel sulfate (NiSO)4·7H2O), 12g/L potassium chloride (KC1), 35g/L boric acid (H)3BO3) 60g/L anhydrous potassium sulfate (K)2SO4) 40g/L of sodium citrate and 0.1g/L of sodium dodecyl sulfate, and the pH value is controlled to be 4.5-5. The cobalt salt gel solution is prepared by mixing about 6g of cobalt nitrate and 2-methylimidazole in the mass percentage of 20: 80 is dissolved in 300ml of methanol, fully stirred and then kept stand to obtain gel liquid.
(3) Preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: ethanol: the molar ratio of stannic chloride is 2: 5: 0.1 of gel solution is coated on the Ni-Co plated film obtained in the step (2)3O4And drying the surface of the carbon fiber substrate of the bottom layer at the controlled temperature of 130 ℃ for 10min, then putting the surface into a muffle furnace, calcining the surface for 20min at the controlled temperature of 300 ℃, repeating the process for 10 times, and calcining the surface for 2h at the last time to obtain the Sn-Co-RuOx intermediate layer.
(4) Preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate plated with the Sn-Co-RuOx middle layer obtained in the step (3) in lead methylsulfonate solution, and controlling the current density of the anode to be 1A/dm2And carrying out electrodeposition for 4 hours at the temperature of 30 ℃ to obtain a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating for 3 hours at the temperature of 100 ℃ to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode. The lead methylsulfonate solution comprises the following components in percentage by weight: 100g/L lead methylsulfonate, 50g/L manganese methylsulfonate, 10g/L ruthenium chloride, 140g/L sodium ethylene diamine tetracetate and 10g/L methanesulfonic acid.
The total thickness of the anode prepared in this example was 2mm, wherein the thickness of the bottom layer was 20 μm, the thickness of the intermediate layer was 10 μm, and the thickness of the active layer was 0.1 mm.
The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material prepared in the embodiment is placed in a manganese chloride electrolyte, and manganese is electrodeposited in an anion exchange membrane electrolytic cell under the electrolysis conditions that the concentration of manganese ions in a cathode electrolyte is 1mol/L, the concentration of ammonium chloride is 2mol/L, the electrolysis temperature is-10 ℃, and the current density is 500A/m2The pH value is 6.10, the concentration of the ammonium chloride in the anolyte is 2mol/L, the hydrochloric acid is 1mol/L, the electrical efficiency is improved by 4 percent compared with the traditional lead-silver alloy anode plate, the cell voltage can be reduced by 20 percent, and the service life is prolonged by 1.2 times.
Example 4
The carbon fiber based amorphous Pb-Mn-RuOx gradient anode material of the embodiment comprises a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer. Wherein Ni-Co3O4Co in composite coating3O4Composition of 10 wt%, Sn in Sn-Co-RuOx plating layer: co: the molar ratio of Ru is 80: 32: 8; pb in the amorphous Pb-Mn-RuOx active layer: mn: the molar ratio of Ru is 70: 48: 2.
the preparation method of the carbon fiber based amorphous Pb-Mn-RuOx gradient anode material comprises the following specific steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, heating the carbon fiber substrate at 400 ℃ under the protection of nitrogen to increase the active specific surface of the carbon fiber and simultaneously avoid the breakage and damage of the carbon fiber in the treatment process, and then placing the carbon fiber substrate at the temperature of 90 ℃ and the mass percent concentration of 20 percent H2SO4Oxidizing for 1 hour in the aqueous solution of (1) to form a striped surface.
(2)Ni-Co3O4Preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a neutral nickel plating solution, controlling the temperature to be 60 ℃, and controlling the cathode current density to be 2A/dm2Electrodepositing for 100min to obtain active nickel, washing with deionized water, immediately placing in cobalt salt gel solution, standing at 80 deg.C for growth4h to obtain a zeolite imidazole framework (ZIF67), and then placing the zeolite imidazole framework in a muffle furnace to be calcined for 2h at the temperature of 600 ℃ to obtain Ni-Co3O4A bottom layer. The neutral nickel plating solution comprises the following components in percentage by weight: 200g/L nickel sulfate (NiSO)4·7H2O), 16g/L potassium chloride (KC1), 33g/L boric acid (H)3BO3) 140g/L anhydrous potassium sulfate (K)2SO4) 60g/L of sodium citrate and 0.4g/L of sodium dodecyl sulfate, and the pH value is controlled to be about 6. The cobalt salt gel solution is prepared by mixing about 6g of cobalt nitrate and 2-methylimidazole according to the mass percentage of 60: 40 is dissolved in 800ml of methanol, fully stirred and then kept stand to obtain gel liquid.
(3) Preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: solvent: the molar ratio of the metal chloride salt is 3: 8: 1 coating the Ni-Co plated film obtained in the step (2) in the gel solution3O4And drying the surface of the carbon fiber substrate of the bottom layer for 10min at the controlled temperature of 130 ℃, then putting the surface into a muffle furnace to calcine for 4min at the controlled temperature of 600 ℃, repeating the process for 10 times, and finally calcining for 2h to obtain the Sn-Co-RuOx intermediate layer. The solvent is a mixture of isopropanol and n-butanol. The metal chloride salt is a mixture of cobalt chloride and ruthenium chloride.
(4) Preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate plated with the Sn-Co-RuOx middle layer obtained in the step (3) in lead methylsulfonate solution, and controlling the current density of the anode to be 4A/dm2And carrying out electrodeposition for 1h at the temperature of 70 ℃ to obtain a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating for 1h at the temperature of 300 ℃ to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode. The lead methylsulfonate solution comprises the following components in percentage by weight: 300g/L lead methylsulfonate, 100g/L manganese methylsulfonate, 20g/L ruthenium chloride, 60g/L complex, sodium ethylene diamine tetracetate and 30g/L methanesulfonic acid. The complex is a mixture of ascorbic acid and sodium acetate.
The total thickness of the anode prepared in this example was 8mm, wherein the thickness of the bottom layer was 200 μm, the thickness of the middle layer was 100 μm, and the thickness of the active layer was 1mm.
The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material prepared in the example is placed in chlorineIn the manganese dissolving electrolyte, the manganese is electrodeposited in an anion exchange membrane electrolytic cell under the electrolysis conditions that the manganese ion concentration of the cathode electrolyte is 1mol/L, the ammonium chloride concentration is 2mol/L, the electrolysis temperature is-10 ℃, and the current density is 500A/m2The pH value is 6.10, the concentration of the ammonium chloride in the anolyte is 2mol/L, the hydrochloric acid is 1mol/L, the electrical efficiency is improved by 6 percent compared with the traditional lead-silver alloy anode plate, the cell voltage can be reduced by 22 percent, and the service life is prolonged by 1.5 times.
Claims (9)
1. The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition is characterized by comprising a carbon fiber substrate and Ni-Co coated on the carbon fiber substrate3O4The substrate comprises a bottom layer, a Sn-Co-RuOx middle layer covering the bottom layer, and an amorphous Pb-Mn-RuOx active layer covering the Sn-Co-RuOx middle layer.
2. The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition as claimed in claim 1, wherein the Ni-Co is selected from the group consisting of3O4The bottom layer is a composite coating, and Co in the composite coating3O4The composition is 2.85-10 wt%; the Sn-Co-RuOx intermediate layer is a plating layer, and the Sn: co: the Ru molar ratio is (54-80): (18-32): (1-10); pb in the amorphous Pb-Mn-RuOx active layer: mn: the Ru molar ratio is (42-70): (24-48): (2-12).
3. The carbon fiber-based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition as claimed in claim 1 or 2, wherein the total thickness of the anode is 2 to 10mm, wherein the thickness of the bottom layer is 20 to 200 μm, the thickness of the intermediate layer is 10 to 100 μm, and the thickness of the active layer is 0.1 to 1mm.
4. The method for preparing the carbon fiber based amorphous Pb-Mn-RuOx gradient anode material for manganese electrodeposition according to any one of claims 1 to 3, characterized by the following method steps:
(1) pretreatment of the carbon fiber matrix: firstly, removing glue, and heating the carbon fiber substrate at 400-800 ℃ under the protection of nitrogen to ensure thatThe active specific surface of the carbon fiber is increased, the breakage and damage of the carbon fiber in the treatment process are avoided, and then the carbon fiber substrate is placed in H with the temperature of 40-90 ℃ and the mass percentage concentration of 10-20%2SO4Oxidizing in the aqueous solution for 1-2 h to enable the surface of the solution to be in a stripe shape;
(2)Ni-Co3O4preparation of the bottom layer: placing the carbon fiber substrate treated in the step (1) in a nickel plating solution, controlling the temperature to be 30-60 ℃, and controlling the cathode current density to be 0.5-2A/dm2Performing electrodeposition for 30-120 min to obtain active nickel, washing with deionized water, immediately placing into a cobalt salt gel solution, standing and growing for 4-8 h at 40-80 ℃ to obtain a zeolite imidazole frame, and then placing into a muffle furnace to control the temperature to be 400-600 ℃ to calcine for 2-6 h to obtain Ni-Co3O4A bottom layer;
(3) preparation of Sn-Co-RuOx interlayer: mixing the mixture containing citric acid: solvent: the molar ratio of the metal chloride is 1-3: 5-8: 0.1-1 gel liquid is coated on the Ni-Co of the carbon fiber substrate treated in the step (2)3O4Drying the surface of the bottom layer for 10min at the temperature of 130 ℃, then putting the bottom layer into a muffle furnace, calcining for 4-20 min at the temperature of 300-500 ℃, repeating the process for 10 times, and calcining for 2h for the last time to obtain an Sn-Co-RuOx intermediate layer;
(4) preparation of amorphous Pb-Mn-RuOx active layer: placing the carbon fiber substrate with the Sn-Co-RuOx intermediate layer obtained after the treatment in the step (3) in a lead methylsulfonate solution, and controlling the current density of the anode to be 1-4A/dm2And carrying out electrodeposition for 1-4 h at the temperature of 30-70 ℃ to obtain a Pb-Mn-RuOx coating, and further carrying out heat treatment on the coating for 1-3 h at the temperature of 100-300 ℃ to obtain an amorphous Pb-Mn-RuOx active layer, namely the carbon fiber-based amorphous Pb-Mn-RuOx gradient anode.
5. The method of claim 4, wherein the nickel plating solution comprises the following components and formula: 150-200 g/L of nickel sulfate, 12-16 g/L of potassium chloride, 30-35 g/L of boric acid, 60-140 g/L of anhydrous potassium sulfate, 40-60 g/L of sodium citrate, 0.1-0.4 g/L of sodium dodecyl sulfate, and the pH value is controlled to be 4.5-6.
6. The preparation method of claim 4, wherein the cobalt salt gel solution is prepared by mixing about 6g of cobalt nitrate and 2-methylimidazole in mass percent (20-60): (40-80) dissolving in 300-800 ml of methanol, fully stirring and standing to obtain the product.
7. The method according to claim 4, wherein the intermediate layer is prepared by using one or two of ethylene glycol, ethanol, isopropanol and n-butanol as a solvent; the metal chloride is tin chloride, cobalt chloride and ruthenium chloride.
8. The method of claim 4, wherein the lead methanesulfonate solution has the following composition and formula: 100-300 g/L lead methylsulfonate, 50-100 g/L manganese methylsulfonate, 10-30 g/L ruthenium chloride, 60-140 g/L complexing agent and 10-30 g/L methanesulfonic acid.
9. The method according to claim 8, wherein the complexing agent is one or more of sodium ethylenediaminetetraacetate, acetylacetone, ascorbic acid, and sodium acetate.
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